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EP2411332B1 - Verwendung von samariummolybdat als anorganisches gelbpigment - Google Patents

Verwendung von samariummolybdat als anorganisches gelbpigment Download PDF

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Publication number
EP2411332B1
EP2411332B1 EP09748855.5A EP09748855A EP2411332B1 EP 2411332 B1 EP2411332 B1 EP 2411332B1 EP 09748855 A EP09748855 A EP 09748855A EP 2411332 B1 EP2411332 B1 EP 2411332B1
Authority
EP
European Patent Office
Prior art keywords
pigment
yellow
moo
pigments
colour
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP09748855.5A
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English (en)
French (fr)
Other versions
EP2411332A1 (de
Inventor
Mundlapudi Lakshmipathi Reddy
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Council of Scientific and Industrial Research CSIR
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Council of Scientific and Industrial Research CSIR
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0003—Compounds of molybdenum
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0009—Pigments for ceramics
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/62—L* (lightness axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/63—Optical properties, e.g. expressed in CIELAB-values a* (red-green axis)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the present invention relates to the use of samarium molybdate Sm 6 MoO 12 as a pigment.
  • Inorganic pigments/colorants are currently widely used in many industries, especially in those of paints, inks, plastics, rubbers, ceramics, enamels, and glasses. These pigments may impart colouristic properties, and protect the coating from the effects of visible as well as ultraviolet and infrared light. For such applications, their properties like chemical and thermal stability, dispersibility, chromaticity, tint strength and covering or masking power are particularly important criteria to be taken into account in the selection of a suitable pigment.
  • Yellow is particularly important colour in the ceramic pigment field and the consumption of the yellow exceeds that of any other coloured pigments.
  • Other yellow ceramic pigments commonly used such as Pb 2 Sb 2 O 7 , PbCrO 4 , CdS are now being expelled from the market because of their toxicity (References may be made to J.A. Badenes, M. Llusar, M.A. Tena, J. Calbo, G. Monros, J. Eur. Ceram. Soc. 2002, 22, 1981-1990 ).
  • the inorganic pigments which are suitable for the above applications and which are in use today on an industrial scale generally comprise of metals like cadmium, lead, chromium, cobalt etc, the use of which is becoming strictly controlled and are even prohibited, by legislation in many countries, due to their high toxicity.
  • metals like cadmium, lead, chromium, cobalt etc
  • the novelty of the present invention is to provide a non-toxic yellow inorganic pigment based on mixed oxides of samarium and molybdenum compounds.
  • the main object of the present invention is thus to use Sm 6 MoO 12 as a yellow inorganic pigment thereby providing a non-toxic yellow inorganic pigment as alternative to the existing toxic yellow pigments, so as they are environmental benign. and a yellow pigment which is commercially viable and obviates the limitations of the Pigment Industry.
  • Another object of the present invention is to to use the pigment to form coloured objects or coatings through their use in applications such as paints, plastics, glasses, ceramics etc.
  • the present invention provides the use of Sm 6 MoO 12 as a yellow inorganic pigment.
  • the particle size of the yellow pigment of formula Sm 6 MoO 12 is in the range of 9.55 ⁇ m to 12.72 ⁇ m.
  • the yellow pigment of formula Sm 6 MoO 12 comprises of a cubic fluorite crystal structure.
  • the samarium molybdate is prepared by a process comprising the steps of mixing the solid solutions of the samarium and molybdenum oxides in the stoichiometric ratios, calcinating at a temperature in the range of 1500° C -1650 ° C in air atmosphere for a period of about 6-12 hrs.
  • Another embodiment of the present invention is the use of samarium molybdate Sm 6 MoO 12 as a yellow inorganic pigment in the coloring of a material, wherein the Sm 6 MoO 12 is added to the material in an amount in the range of 5 % to 10 % by weight.
  • material is selected from the group of organic polymers such as plastics, glasses, ceramics, paints etc.
  • the samarium molybdenum yellow pigments having formula Sm 6 MoO 12 comprising of a cubic crystal structure.
  • These inorganic pigments are formed by mixing stoichiometric amounts of high purity (NH 4 ) 6 Mo 7 O 24 .4H 2 O and Sm 2 O 3 ; ball milled and calcined at a temperature in the range of 1500-1650° C for 10-12 hrs in air.
  • the well ground calcined powders were used for the characterization of pigments.
  • the particle size distribution of the pigment, Sm 6 MoO 12 was investigated in water as a medium and calgon as the dispersing agent measured by the laser scattering particle size distribution analyser (CILAS 930 Liquid). The results show a distribution with 90% of the particles being smaller than 28.63 ⁇ m, 50% smaller than 9.55 ⁇ m and 10% smaller than 1.25 ⁇ m.
  • the mean particle diameter of the pigment sample was found to be 12.72 ⁇ m.
  • Thermogravimetric analysis of the typical pigment Sm 6 MoO 12 was carried out in the range of 50-1000° C using Pyris Diamond TG/DTA Perkin Elmer make. It is clear from the thermogram that the pigment is thermally stable up to 1000° C.
  • the typical pigment Sm 6 MoO 12 was tested for its acid and alkali resistance. A pre-weighed quantity of the pigment was treated with 3% HCl/H 2 SO 4 /HNO 3 and NaOH, and soaked for half an hour with constant stirring using a magnetic stirrer. The pigments were then filtered, washed with water, dried and weighed. No weight loss was noticed for all the acids and alkali tested.
  • a further aspect of the present invention is to provide colouring to a substrate (like plastics, polymers etc.).
  • the method includes the steps of providing a substrate, and adding a samarium molybdate yellow pigment to the substrate.
  • the samarium molybdate yellow pigment may be dispersed in the substrate or coated on the substrate.
  • Thermogravimetric analysis of the pigmented polymer sample was carried out in the range of 50-500° C.
  • the thermogravimetric analysis clearly indicates the thermally stability of the coloured polymer up to 225° C.
  • the light resistance of the above Sm 6 MoO 12 dispersed PMMA matrix was tested by exposing it to sunlight at various time intervals and measured the colour coordinates.
  • the sharp and intense peaks reveal the crystalline nature of the pigment.
  • Optical reflectance of the powder was measured with UV-vis spectrophotometer (Shimadzu, UV-2450) using barium sulphate as a reference and is shown in Figure 2 .
  • the optical absorption edge critically depends on the concentration of molybdenum present in the pigment samples and it absorbs blue light efficiently, which is originated from the O 2p -Mo 3d charge transitions. As a result, the colour of the pigment samples becomes yellow because blue is a complimentary colour to yellow.
  • the values a * (the axis red-green) and b * (the axis yellow-blue) indicate the color hue.
  • the value L * represents the lightness or darkness of the color as related to a neutral grey scale.
  • Thermogravimetric analysis of the typical pigment Sm 6 MoO 12 was carried out in the range of 50-1000° C using Pyris Diamond TG/DTA Perkin Elmer make. It is clear from the thermogram that the pigment is thermally stable up to 1000° C.
  • the typical pigment Sm 6 MoO 12 was tested for its acid and alkali resistance. A pre-weighed quantity of the pigment was treated with 3% HCl/H 2 SO 4 /HNO 3 and NaOH, and soaked for half an hour with constant stirring using a magnetic stirrer. The pigments were then filtered, washed with water, dried and weighed. No weight loss was noticed for all the acids and alkali tested.
  • the optical absorption edge critically depends on the concentration of molybdenum present in the pigment samples and it absorbs blue light efficiently, which is originated from the O 2p -Mo 3d charge transitions. As a result, the colour of the pigment samples becomes yellow because blue is a complimentary colour to yellow.
  • the values a * (the axis red-green) and b * (the axis yellow-blue) indicate the color hue.
  • the value L * represents the lightness or darkness of the color as related to a neutral grey scale.
  • the colour hue values obtained are more or less the same, indicating the uniform distribution of the pigment particles in the polymer matrix.
  • the intensity of the colour of the plastic depends on the concentration of the pigment being incorporated.
  • Thermogravimetric analysis of the pigmented polymer sample was carried out in the range of 50-500° C.
  • the thermogravimetric analysis clearly indicates the thermally stability of the coloured polymer up to 225° C.
  • the light resistance of the above Sm 6 MoO 12 dispersed PMMA matrix was tested by exposing it to sunlight at various time intervals and measured the colour coordinates.
  • the colour hue values obtained are more or less the same, indicating the uniform distribution of the pigment particles in the polymer matrix.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Paints Or Removers (AREA)

Claims (3)

  1. Verwendung von Samariummolybdat Sm6MoO12 als anorganisches Gelbpigment.
  2. Verwendung nach Anspruch 1 bei der Einfärbung eines Materials, wobei das Sm6MoO12 dem Material in einer Menge im Bereich von 5 bis 10 Gew.-% zugesetzt wird.
  3. Verwendung nach Anspruch 2, wobei das Material aus der Gruppe bestehend aus Kunststoff, Glas, Keramik und Anstrichmittel ausgewählt ist.
EP09748855.5A 2009-03-27 2009-09-30 Verwendung von samariummolybdat als anorganisches gelbpigment Not-in-force EP2411332B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN601DE2009 2009-03-27
PCT/IN2009/000541 WO2010109473A1 (en) 2009-03-27 2009-09-30 A novel yellow inorganic pigment from samarium and molybdenum compounds and a process for preparing the same

Publications (2)

Publication Number Publication Date
EP2411332A1 EP2411332A1 (de) 2012-02-01
EP2411332B1 true EP2411332B1 (de) 2017-03-15

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EP09748855.5A Not-in-force EP2411332B1 (de) 2009-03-27 2009-09-30 Verwendung von samariummolybdat als anorganisches gelbpigment

Country Status (8)

Country Link
US (1) US8303706B2 (de)
EP (1) EP2411332B1 (de)
JP (1) JP5404905B2 (de)
CN (1) CN102414128B (de)
AU (1) AU2009343120B2 (de)
BR (1) BRPI0924476A2 (de)
RU (1) RU2528668C2 (de)
WO (1) WO2010109473A1 (de)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102432056B (zh) * 2011-10-13 2013-08-14 陕西科技大学 一种溶剂热法制备Sm2O3 纳米晶的方法
MA35368B1 (fr) 2013-01-09 2014-09-01 Taibah University Méthode de synthèse de précurseurs pour la production de l'oxyde de molybdène moo3 et de matériaux conséquents
US9891350B2 (en) 2014-02-17 2018-02-13 Eastman Kodak Company Light blocking articles having opacifying layers
CN108084734A (zh) * 2016-11-21 2018-05-29 上海华明高技术（集团）有限公司 一种耐高温黄色陶瓷色料及其制备方法
CN111205674B (zh) * 2020-01-20 2021-11-09 大连交通大学 陶瓷颜料组合物、黄色玻璃陶瓷颜料、玻璃陶瓷及其制备方法
CN116102055B (zh) * 2022-11-25 2024-08-23 中国科学院长春应用化学研究所 一种稀土复合氧化物着色剂及其制备方法

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US2992123A (en) 1959-04-20 1961-07-11 Harshaw Chem Corp Yellow ceramic pigments
DE1211137B (de) * 1962-11-15 1966-02-24 Atomic Energy Commission Verfahren zur Herstellung von Wolfram oder Molybdaen enthaltenden Oxyden
US3300848A (en) * 1963-12-24 1967-01-31 Jr Carl F Leitten Method of preparing oxides for neutronic reactor control
NL9200293A (nl) 1992-02-18 1993-09-16 Colorsil Bv Gedoteerd zirkoonmengsilicaatpigment, werkwijze voor het bereiden daarvan, alsmede produkten die een dergelijk of een aldus bereid pigment bevatten.
US5316570A (en) 1992-09-28 1994-05-31 Ferro Corporation Stable heavy metal free zircon pigments for use in plastics and paints and method for coloring thereof
FR2712596B1 (fr) 1993-11-18 1996-03-08 Rhone Poulenc Chimie Pigments à base d'oxyde de zirconium et de cérium, de praséodyme et/ou de terbium, leur procédé de préparation et leur utilisation.
US5693102A (en) 1995-09-27 1997-12-02 Cerdec Aktiengesellschaft Keramische Farben Oxonitrides of the formula LnTaON2 with enhanced brightness and a process for their use
FR2750415B1 (fr) 1996-06-28 1999-08-27 Rhone Poulenc Chimie Molybdate de cerium et d'alcalin ou d'alcalino-terreux, son procede de preparation et son utilisation comme pigment colorant
FR2767129B1 (fr) 1997-08-08 1999-09-17 Rhodia Chimie Sa Composition a base d'un sesquisulfure de samarium, procede de preparation et utilisation comme pigment colorant
JP3954837B2 (ja) 2001-11-28 2007-08-08 株式会社ファインラバー研究所 黄色系セリウム顔料
RU2315072C1 (ru) * 2006-06-19 2008-01-20 Институт неорганической химии А.В. Николаева Сибирского отделения Российской академии наук Неорганический пигмент на основе молибдата
CN101260250B (zh) 2007-02-26 2015-12-02 科学与工业研究委员会 黄色无机颜料及其制备方法

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Also Published As

Publication number Publication date
EP2411332A1 (de) 2012-02-01
AU2009343120A1 (en) 2011-10-20
BRPI0924476A2 (pt) 2016-02-16
US8303706B2 (en) 2012-11-06
JP2012521944A (ja) 2012-09-20
RU2011143354A (ru) 2013-05-10
JP5404905B2 (ja) 2014-02-05
WO2010109473A1 (en) 2010-09-30
CN102414128B (zh) 2014-02-12
CN102414128A (zh) 2012-04-11
RU2528668C2 (ru) 2014-09-20
AU2009343120B2 (en) 2014-04-17
US20120017807A1 (en) 2012-01-26

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